Modifications of Plant Oils for Value-Added Uses - ACS Symposium

Chapter 15

Downloaded by UNIV OF CALIFORNIA SAN DIEGO on August 20, 2015 | http://pubs.acs.org Publication Date (Web): June 18, 2015 | doi: 10.1021/bk-2015-1192.ch015

Modifications of Plant Oils for Value-Added Uses H. N. Cheng*,1 and Atanu Biswas2 1Southern

Regional Research Center, USDA Agricultural Research Service, 1100 Robert E. Lee Boulevard, New Orleans, Louisiana 71024, U.S.A. 2National Center for Agricultural Utilization Research, USDA Agricultural Research Service, Peoria, Illinois 61604, U.S.A. *E-mail: [email protected].

Plant oils are valuable agricultural commodities and useful raw materials for the preparation of value-added products. In this article, a review is made of the various structural modifications made on plant oils in the authors’ laboratories. The reactions include Diels-Alder, ene reaction, transesterification, acid or enzymatic hydrolysis, heat-bodying reaction, hydrogenation, epoxidation, formation of acetonide, aminohydrin, and azidohydrin, click reaction, and polymerization. A wide range of products have been made from plant oils and their epoxidized derivatives. Many of these reaction pathways produce new triglyceride structures not previously reported. The properties of selected products have been tested, particularly in lubricant applications to enhance viscosity, thermal stability, or mechanical wear.

Introduction In addition to being important items for food and agriculture, plant oils are also useful renewable raw material for the development of novel substances (1, 2). Current interest in this field of research is high. Some examples of modified vegetable oils are epoxidized oil (3, 4), soybean oil methyl ester (methyl soyate) (5, 6), maleated products (7, 8), and soybean oil polymers (9–11). Applications Not subject to U.S. Copyright. Published 2015 by American Chemical Society In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


include lubricants (12), paints, coatings, and adhesives (13, 14), plastics (15, 16), and biomedical materials (13). Several recent review articles are available (12–18). For many years the present authors and their collaborators at USDA have been active in this area. In this article, a review is being conducted of some of the work done in their laboratories. A schematic summary of the reaction pathways is provided in Figure 1.

Figure 1. Scheme of the modification and polymerization reactions conducted on triglycerides (TG) by the authors and their collaborators in the past 8 years.

Reactions Directly with Triglycerides The reality of the current market for chemical products is that they are pricecompetitive. In product development, it would be desirable (wherever possible) to decrease the number of reaction steps in order to save on processing cost. One way to achieve the cost reduction is to make products directly from plant oils. Several examples of these reactions are given below.

Pericyclic Reactions - Polymer Formation Pericyclic reactions include Diels-Alder and ene reactions (19, 20). The present authors have found these reactions to be particularly useful in generating new triglyceride derivatives and new polymers from plant oils. Thus, in a recent paper (21), they studied the reaction of soybean oil (SBO) with 4-phenyl-1,2-4-triazoline-3,5-dione (PTAD). The reaction schemes are shown in Figure 2. 236 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 2. Reaction schemes for oleate and linoleate with the reaction of PTAD.

The process required no solvent or catalyst and entailed only the mixing of triglyceride and PTAD. 1H NMR was used to determine the chemical structures generated from oleate and linoleate and to monitor the reactions. In the PTAD reaction, both ene (structures A, B, C) and Diels-Alder (structure D) products were 237 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


found. Higher PTAD used in the reaction produced higher yields of all products. With increasing temperature, the yield of B increased slightly, that of C decreased slightly, and that of D increased more noticeably. Owing to polymer formation, the reaction product mixture exhibited a self-curing behavior as a function of time. Thus, the viscosity of a mixture containing PTAD and soybean oil in a 3:10 weight ratio increased 40-fold in about 2 h at room temperature, suggesting its possible use as an additive in lubricants, caulking, cement and thickener applications. A related reaction entailed diethyl azodicarboxylate (DEAD) (22). DEAD and SBO were mixed together in the absence of catalyst and solvent. In a microwave oven the reaction was achieved in 5–15 minutes at 90-110ºC. (The reaction could also be conducted using conventional heat.) Interestingly, in this case only ene reaction products (e.g., structure E) were found (Figure 3). This reaction product mixture also exhibited a self-curing behavior as a function of time (23), although not as fast as the reaction involving PTAD.

Figure 3. Schematic diagram for the reaction of soybean oil with DEAD. Structure E is a generic representation, where the DEAD moiety can be attached to different carbons at α positions to the double bonds in the product. It may be noted that most of the current lubricants originate from petroleum stock, which may make them environmentally less friendly and more difficult to dispose of. Plant oils are good platforms for new products that can substitute for conventional mineral oil-based lubricating oils and synthetic esters. Pericyclic Reactions - Other Derivatives In the previous section, it was shown that the pericyclic reaction of SBO and DEAD produced SBO-aza-dicarboxylate ester (structure E). In another paper 238 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


(24), it was also shown that the alkaline and the enzymatic hydrolysis of this product produced different products (Figure 4). Thus, lipase hydrolysis cleaved the glycerol from the triglyceride to generate the fatty acid-aza-dicarboxylate (G). Hydrolysis with NaOH, however, produced the hydrazine derivative of the fatty acids (H).

Figure 4. Enzymatic and alkaline hydrolysis of soybean oil-DEAD adduct. Other derivatives of SBO-aza-dicarboxylate ester (E) may also be of interest. This compound can be subjected to transesterification with methanol, similar to the formation of methyl soyate (25). Thus, the addition of a lipase to a mixture of SBO, methanol, and water enabled this reaction to occur, as shown in Figure 5. The reaction shown in Figure 5 can decrease the molecular weight of the SBODEAD reaction product, and thereby its viscosity. As noted in the previous section, the SBO-DEAD product can undergo self-curing reaction with substantial increase in viscosity. Thus, the combination of self-curing reaction and transesterification with methanol can permit a range of viscosities to be achieved, depending on the specific need of the end-use application. Other compounds can be synthesized through transesterification with polyols. Two examples of enzyme-catalyzed reactions are shown in Figure 6 for glycerol and poly(ethylene glycol) (PEG) (25). In both cases, surfactant-like structures were produced, each with a fatty acid derivative coupled to a water-soluble moiety. Other Triglyceride Derivatives Plant oils typically contain olefins and esters, both of which can be modified to form different derivatives. In fact, the number of possibilities to derivatize triglycerides is very large and limited only by the researcher’s creativity and availability of time and manpower. Two examples from the authors’ work can be cited here. In the first example, SBO was subjected to microwave-irradiation (MI) and heat bodying (HB) at 200–250ºC for 20–60 min (26). Both procedures produced increased viscosity compared with untreated SBO. Pour point decreased 239 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


from −9ºC for the untreated SBO, −15ºC for the HB oil, and −18ºC for the MI oil despite viscosity increases. Pressurized DSC analysis showed higher oxidative stability for HB oil with even higher stability for MI oil. MI treatment improved the cold-flow behavior of SBO but reduced its potential as a lubricant.

Figure 5. Enzyme-catalyzed transesterification of SBO-DEAD adduct with methanol.

Figure 6. Two examples of enzymatic transesterification with polyols. 240 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


In the second example, hydrogenation was applied to cottonseed oil. Eleven catalysts based on Ni, Pd, and Pt from two manufacturers were used for hydrogenating cottonseed oil, with the goal of minimizing trans fatty acid (TFA) content (27). Despite different temperatures, catalyst levels, and reaction times being used, the data from each catalyst type fell on the same curve when the TFA level was plotted against the iodine value (IV). Under low-pressure, high-mixing hydrogenation conditions, Ni, Pd, and Pt catalysts all produced 5% TFA and 5% stearic acid at 95 IV; however, at 70 IV, only Pt catalysts produced 9% TFA and about 17% stearic acid. Kinetic modeling provided a better understanding of the relative reaction rates involved in hydrogenation. Pt catalysts converted linoleic and oleic acids more slowly to TFA and quickly hydrogenated TFA, thereby leading to low TFA levels. Furthermore, in a direct comparison of hydrogenated soybean oil and cottonseed oil, lower TFA and stearic levels were found with hydrogenated cottonseed oil (28).

Polymers Directly from Triglycerides In the last section it was mentioned that soybean oil and cottonseed oil were hydrogenated at different levels using commercial Ni, Pt and Pd catalysts under different hydrogenation conditions. Since the reactivity of plant oils often depends on the amount and the type of olefins present, the ability to vary the olefin type and amount is useful in generating targeted triglyceride derivatives. This possibility was pointed out in a recent report (29). A preliminary study of the thermal polymerization of soybean oil, cottonseed oil, and hydrogenated cottonseed oil (carried out at 330 °C for 6 hours in nitrogen) produced polymers with viscosities in decreasing order: soybean oil polymer > cottonseed oil polymer > polymer derived from cottonseed oil that had been hydrogenated to IV 97. These viscosity results for the polymers are consistent with the amounts of unsaturation present in the starting oils. Appropriate blending of hydrogenated and/or unhydrogenated triglyceride oils may also be used for polymerization to optimize the properties of the resulting products.

Reactions with Epoxidized Triglycerides It is well known that plant oils can be epoxidized; in fact, epoxidized soybean oil is a commercial product and employed as a poly(vinyl chloride) plasticizer, among other applications. Because the epoxidized soybean oil is commercially available, it is a useful synthon for the development of additional products, as shown in the examples below.

Triglyceride Acetonide In the first example, a new type of branched soybean oil and its methyl ester was made that involved the formation of acetonides from epoxide (30) (Figure 7). 241 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 7. Formation of acetonide from epoxidized triglyceride.

The procedure entailed the room-temperature reaction in the presence of ferric chloride catalyst and was found to be facile and environmentally friendly. The products were fully characterized with the help of model compounds, including elemental analysis, IR, NMR, and GC-MS. From the analytical results, it appeared that the reaction could readily be used to make acetonides out of soybean oil, methyl soyate, methyl linoleate, and methyl oleate. There are many advantages of this reaction. First, the acetonide reaction produces a branched fatty acid moiety, which can provide improved properties for methyl soyate and soybean oil. Secondly, the reaction is catalyzed by ferric chloride, which is less likely to cause hydrolysis of the ester or the glyceride. Thirdly, the use of room temperature results in reduced energy usage. Finally, acetone is inexpensive and has a good environmental profile. Triglyceride Aminohydrin One of the interesting reactions is to convert the epoxide functionality into aminohydrin. Thus, a facile (and environmentally friendly) reaction was discovered between epoxidized methyl oleate and aniline to produce an oleate-aniline adduct, without the formation of fatty amide (31) (Figure 8).

Figure 8. Conversion of epoxide to aminohydrin with the aid of ionic liquids (IL).

The reaction shown in Figure 8 was carried out neat, with a catalytic amount of an ionic liquid. No solvent was used, no byproducts were produced, and the ionic liquid could be recovered and recycled. The reaction products were fully characterized by NMR and GC-MS. Subsequent work indicated that a triglyceride 242 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


modified with aniline improved its thermal stability and mechanical wear for the lubricant application (32). The advantages of this reaction are that it is easily performed, gives good yield, and requires only a small amount of ionic liquid as a catalyst. The reaction is a good method to introduce an aromatic amine onto the fatty acid structure. A variation of this study is the addition of diethylamine onto epoxidized oil, using ZnCl2 as a catalyst (Figure 9) (33). In this case, an aliphatic aminohydrin is obtained.

Figure 9. Reaction of epoxide with diethylamine in the presence of ZnCl2.

Triglyceride Azidohydrin and Its Click Derivatives Another interesting reaction is to convert the epoxide functionality into azidohydrin, also with the help of an ionic liquid (34) (Figure 10).

Figure 10. Conversion of epoxide to azidohydrin with the aid of ionic liquids (IL).

The azidization reaction was carried out in water with only a small amount of an ionic liquid as a catalyst. The distribution of azide and alcohol functionalities on the fatty acid moiety was approximately random. This reaction was applied to methyl oleate, methyl linoleate, soybean oil, and methyl soyate, and high yields were observed. The resulting chemical structures were confirmed by 13C NMR. In addition, the azide product was subjected to the click reaction with phenylacetylene (Figure 11) (35). The reaction was relatively easy to do and gave high yields. The click reaction turned out to be a convenient method to attach an acetylene-containing moiety (phenylacetylene, in this case) onto a fatty ester or a triglyceride. 243 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 11. Click reaction between azidohydrin and phenylacetylene.

Polymers from Epoxidized Triglyceride Liu and Erhan showed earlier that the use of BF3-etherate could polymerize epoxidized soybean oil into an insoluble material (36). It was noted that the product could be converted into hydrogels by saponification for possible use in personal care. Subsequently Liu and Biswas (37) showed that fluoroantimonic acid hexahydrate could be employed as a catalyst in ethyl acetate. More recent work suggested that fluorosulfonic acid was also a potent catalyst for the polymerization of vernonia oil (38) and soybean oil (39). In addition, furan-like structure can be produced, which can undergo Diels-Alder reaction to produce further derivatives (40).

Conclusions and Perspectives Plant oils are valuable agricultural commodities and useful raw materials for the preparation of value-added products. In this article, a review is made of the various structural modifications made on plant oils in the authors’ laboratories. A wide range of products have been made from plant oils and their epoxidized derivatives. The reactions include Diels-Alder, ene reaction, transesterification, acid or enzymatic hydrolysis, heat-bodying reaction, hydrogenation, epoxidation, formation of acetonide, aminohydrin, azidohydrin, click reaction, and polymerization. Some of these products are useful in lubricants to enhance viscosity, thermal stability, or mechanical wear. Yet, these products serve only as harbingers for what can potentially be done. With proper incentives and further efforts, many more new reaction pathways and new structures can surely be produced in the future. Further products may also be possible but require appropriate applications development and customer input. A key determinant in the future growth of plant oils as raw materials for industrial products is the price and the availability of plant oils relative to petroleum crude. Currently petroleum-based products still dominate the market. Because of their extended time of use, the manufacturing facilities are already in place to produce the petroleum-based products, and the companies have qualified 244 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


those products for various applications. Nonetheless, with increasing awareness of the need for sustainability, environmental stewardship, and green chemistry in the future, the use of agri-based, renewable raw materials is expected to increase in the future, but it will take time to slowly replace the well-entrenched petroleum-based products. Whereas the public support of sustainability can encourage increased R&D in this area, ultimately the long-term commercial prospect of triglyceride-based products will depend on the ease of use and the cost effectiveness of the new products, the success of marketing, the response from manufacturers of petroleum-based products, and other business-related considerations.

Acknowledgments Thanks are due to many collaborators over the years whose names appear in the publications cited. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.

References 1. 2. 3.

4.

5. 6. 7.

8.

9.

Karak, N. Vegetable Oil-Based Polymers; Woodhead Publishing: Cambridge, U.K., 2012. Erhan, S. Z. Industrial Uses of Vegetable Oils; AOCS Press: Champaign, Illinois, U.S.A., 2005. Petrovic, Z. S.; Zlatanic, A.; Lava, C. C.; Sinadinovic-Fiser, S. Epoxidation of soybean oil in toluene with peroxoacetic and peroxoformic acids: kinetics and side reactions. Eur. J. Lipid Sci.Technol. 2002, 104, 293–299. Kuo, M. C.; Chou, T. C. Kinetics and mechanism of the catalyzed epoxidation of oleic acid with oxygen in the presence of benzaldehyde. Ind. Eng. Chem. Res. 1987, 26, 277–284. Knothe, G. Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters. Fuel Process. Technol. 2005, 86, 1059–1070. Srivastava, A.; Prasad, R. Triglycerides-based diesel fuels. Renewable Sustainable Energy Rev. 2000, 4, 111–133. Warth, H.; Mulhaupt, R.; Hoffmann, B.; Lawson, S. Polyester networks based upon epoxidized and maleinated natural oils. Angew. Makromol. Chem. 1997, 249, 79–92. Tran, P.; Seybold, K.; Graiver, D.; Narayan, R. Free radical maleation of soybean oil via a single-step process. J. Am. Oil Chem. Soc. 2005, 82, 189–194. Li, F.; Hanson, M. V.; Larock, R. C. Soybean oil-divinylbenzene thermosetting polymers: R. C. Soybean oil-divinylbenzene thermosetting polymers: synthesis, structure, properties and their relationships. Polymer 2001, 42, 1567–1579. 245 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


10. Sharma, V.; Kundu, P. P. Addition polymers from natural oils: a review. Prog. Polym. Sci. (Oxford) 2006, 31, 983–1008. 11. Khot, S. N.; Lascala, J. J.; Can, E.; Morye, S. S.; Williams, G. I.; Palmese, G. R.; Kusefoglu, S. H.; Wool, R. P. Development and application of triglyceride-based polymers and composites. J. Appl. Polym. Sci. 2001, 82, 703–723. 12. Soni, S.; Agarwal, M. Lubricants from renewable energy sources – a review. Green Chem. Lett. Rev. 2014, 7, 359–382. 13. Lligadas, G.; Ronda, J. C.; Galià, M.; Cádiz, V. Renewable polymeric materials from vegetable oils: a perspective. Mater. Today 2013, 16, 337–343. 14. United Soybean Board. Soy-based paints and coatings; http://soynewuses.org/wp-content/uploads/44422_TDR_PaintsCoatings.pdf (accessed on January 20, 2015). 15. Xia Y., ; Larock, R. C. Vegetable oil-based polymeric materials: synthesis, properties, and applications. Green Chem. 2010, 12, 1893–1909. 16. Guner, S. F.; Yagci, Y.; Erciyes, A. T. Polymers from triglyceride oils. Prog. Polym. Sci. 2006, 31, 633–670. 17. Biswas, A.; Sharma, B. K.; Willett, J. L.; Erhan, S. Z.; Cheng, H. N. Soybean oil as a renewable feedstock for nitrogen-containing derivatives. Energy Environ. Sci. 2008, 1, 639–644. 18. Meier, A. R. M.; Metzger, J. O.; Schubert, U. S. Plant oil renewable resources as green alternatives in polymer science. Chem. Soc. Rev. 2007, 36, 1788–1902. 19. Fleming, I. Pericyclic Reactions; Oxford University Press: Oxford, 1998. 20. Sankararaman, S. Pericyclic Reactions - A Textbook, 1st ed; Wiley-VCH: Weinheim, 2005. 21. Biswas, A.; Cheng, H. N.; Kim, S.; Liu, Z. Modified triglyceride oil through reactions with phenyltriazolinedione. J. Am. Oil Chem. Soc. 2014, 91, 125–131. 22. Biswas, A.; Sharma, B. K.; Willett, J. L.; Vermillion, K.; Erhan, S. Z.; Cheng, H. N. Novel modified soybean oil containing hydrazino-ester: synthesis and characterization. Green Chem. 2007, 9, 85–89. 23. Biswas, A.; Sharma, B. K.; Willett, J. L.; Erhan, S. Z.; Cheng, H. N. Roomtemperature self-curing ene reactions involving soybean oil. Green Chem. 2008, 10, 298–303. 24. Biswas, A.; Shogren, R. L.; Woods, K. K.; Erhan, S. Z.; Cheng, H. N. New bio-based materials from soybean oil: hydrazine and related derivatives. ACS Polym. Prepr. 2006, 47, 259–260. 25. Biswas, A.; Shogren, R. L.; Willett, J. L.; Erhan, S. Z.; Cheng, H. N. Enzymatic Products from Modified Soybean Oil Containing Hydrazinoester. ACS Symp. Series 2008, 999, 76–85. 26. Biswas, A.; Adhvaryu, A.; Stevenson, D. G.; Sharma, B. K.; Willett, J. L.; Erhan, S. Z. Microwave irradiation effects on the structure, viscosity, thermal properties and lubricity of soybean oil. Ind. Crops Prod. 2007, 25, 1–7. 27. Cheng, H. N.; Dowd, M. K.; Easson, M. W.; Condon, B. D. Hydrogenation of Cottonseed Oil wi B.D. Hydrogenation of Cottonseed Oil with Nickel, 246 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

28.

29.


30.

31.

32.

33.

34.

35.

36. 37.

38.

39.

40.

Palladium and Platinum Catalysts. J. Am. Oil Chem. Soc. 2012, 89, 1557–1566. Cheng, H. N.; Rau, M. W.; Dowd, M. K.; Easson, M. W.; Condon, B. D. Comparison of Soybean and Cottonseed Oils upon Hydrogenation with Nickel, Palladium and Platinum Catalysts. J. Am. Oil Chem. Soc. 2014, 91, 1461–1469. Cheng, H. N.; Rau, M.; Dowd, M. K.; Easson, M. W.; Condon, B. D. Hydrogenated cottonseed oil as raw material for biobased materials. ACS Symp. Ser. 2013, 1144, 359–371. Biswas, A.; Sharma, B. K.; Vermillion, K.; Willett, J. L.; Cheng, H. N. Synthesis of Cyclic Ketal from Soybean Oil and Fatty Esters. J. Agric. Food Chem. 2011, 59, 3066–3070. Biswas, A.; Sharma, B. K.; Doll, K.; Willett, J. L.; Erhan, S. Z.; Vermillion, K.; Cheng, H. N. Synthesis of an Amine-Oleate Derivative Using an Ionic Catalyst. J. Agric. Food Chem. 2009, 57, 8136–8141. Biswas, A., Doll, K.; Cheng, H. N.; Sharma, B. K.. Process for preparation of nitrogen-containing vegetable oil-based lubricant additive. U.S. Patent 8,841,470, September 23, 2014. Biswas, A.; Adhvaryu, A.; Gordon, S. H.; Erhan, S. Z.; Willett, J. L. Synthesis of diethylamine functionalized soybean oils. J. Agric. Food Chem. 2005, 53, 9485–9490. Biswas, A.; Sharma, B. K.; Willett, J. L.; Adhvaryu, A.; Erhan, S. Z.; Cheng, H. N. Azide Derivatives of Soybean Oil and Fatty Esters. J. Agric. Food Chem. 2008, 56, 5611–5616. Biswas, A.; Sharma, B. K.; Klasson, K. T.; Cheng, H. N. New Bio-Based Materials From Vegetable Oil: Amination and Click Reactions. ACS Polym. Prepr. 2011, 52, 78–79. Liu, Z.; Erhan, S. Z. Ring-opening Polymerization of Epoxidized Soybean Oil. J. Am. Oil Chem. Soc. 2010, 87, 437–444. Liu, Z.; Biswas, A. Fluoroantimonic acid hexahydrate (HSbF6-6H2O) catalysis: The ring-opening polymerization of epoxidized soybean oil. Appl. Catal., A 2013, 453, 370–375. Biswas, A.; Cheng, H. N.; Klasson, K. T.; Liu, Z.; Berfield, J.; Ayorinde, F. O. Direct polymerization of vernonia oil through cationic means. J. Am. Oil Chem. Soc. 2014, 91, 2111–2116. Biswas, A.; Liu, Z.; Cheng, H. N. Polymerization of Epoxidized Triglyceride with Fluorosulfonic Acid. Int. J. Polym. Anal. Charact. Submitted for publication. Biswas, A.; Liu, Z.; Berfield, J. L.; Cheng, H. N. Synthesis of Novel Plant Oil Derivatives: Furan and Diels-Alder Reaction Products. Int. J. Agric. Sci. Technol. Accepted for publication.

247 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Modifications of Plant Oils for Value-Added Uses - ACS Symposium

Recommend Documents